CA2016416A1 - Liquid/liquid catalytic sweetening process - Google Patents
Liquid/liquid catalytic sweetening processInfo
- Publication number
- CA2016416A1 CA2016416A1 CA002016416A CA2016416A CA2016416A1 CA 2016416 A1 CA2016416 A1 CA 2016416A1 CA 002016416 A CA002016416 A CA 002016416A CA 2016416 A CA2016416 A CA 2016416A CA 2016416 A1 CA2016416 A1 CA 2016416A1
- Authority
- CA
- Canada
- Prior art keywords
- quaternary ammonium
- ammonium compound
- hydroxide
- liquid
- phthalocyanine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/06—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of alkaline solutions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
"IMPROVED LIQUID/LIQUID CATALYTIC SWEETENING PROCESS"
ABSTRACT
A liquid/liquid sweetening process for catalytically oxidizing mercaptans in a sour hydrocarbon fraction is improved by the addition of a quaternary ammonium compound to the alkaline solution which contains a metal chelate catalyst such as a metal phthalocyanine and which in combination with an oxidizing agent has been used in the prior art as the sweetening agent. A
preferred type of quaternary ammonium compound is a surfactant quaternary ammonium compound. A synergistic effect between the quaternary ammonium compound and the metal chelate is observed.
ABSTRACT
A liquid/liquid sweetening process for catalytically oxidizing mercaptans in a sour hydrocarbon fraction is improved by the addition of a quaternary ammonium compound to the alkaline solution which contains a metal chelate catalyst such as a metal phthalocyanine and which in combination with an oxidizing agent has been used in the prior art as the sweetening agent. A
preferred type of quaternary ammonium compound is a surfactant quaternary ammonium compound. A synergistic effect between the quaternary ammonium compound and the metal chelate is observed.
Description
IMPROYEE) LIQUID~LLIQUID C:ATALYTiÇ swEE~rENlNG PRO~SS"
BACKGROUND OF THE INVENTION
Processss for the treatm~nt of a sour hydrocarbon fraetion wh~r0 the fraction is treatecl by contactin~ it with ~n oxidation catalyst and an alkaline5 agent in the presence of an oxidizin~ agent at r~action conditions have becomewcll known and widely practic0d in the p~roleum refinin~ industry. These pro-cesses are typically designed to ~ffsct th~ sxidation of offensive mercaptans contained in a sour hydrocarbon fraction to innocuous disulfides - a process commonly re~0rred to as sweetening. The oxidizing agent is mos~ often air.
o Gasoline, including natural, straight run and cracked gasolinesj is the rnost fre-quently treated sour hydrocarbon fraction. Other sour hydrocarbon fractions which can be treated include 2he normally gaseous petroleum fraction as well as naphtha, kerosene, Jet fuel, fuel oil, and th~ like.
A commoniy used eon~inuous process for catalytically treatiny sour 15 hydrocarbon ~ractions entails contacting the fraction with a metal phthalocyanine catalyst dispersed in an aqusous caustic solution to yield a doctor sweet product. The sour fraction and the catalyst containing aqueous caustic solution provide a liquid-liquid system wherein mercaptans are converted to disulfidss at the interface of the immisGible solutions in the 20 presence of an oxidizing agen~--usually air. The prior art shows that catalysts such as metal phthalocyanines can b~ used to oxidize th~ m~rcaptans. ~, .~, U.S. Patent No. 2,999,806.
It has b~en ~ound that adding a quaternary ammonium compound to the caustic or alkaline solution used in such a process enhances the ability of the 25 oxidation catalyst to convert the mercaptans to disulfides. In particular, applicants have discovered that a preferred quaternary ammonium compound is a surfactant ~uaternary ammonium compound. Althou~h quaternary ammonium compounds have heretofor~ been used in sweetening sour hydrocarbon ~ractions, they have been used in eonjunction with fixed bed 30 catalysts, ~.g., a metal phthalocyanine dspositcd on an activated charcoal.
;"
.
.
.
.
BACKGROUND OF THE INVENTION
Processss for the treatm~nt of a sour hydrocarbon fraetion wh~r0 the fraction is treatecl by contactin~ it with ~n oxidation catalyst and an alkaline5 agent in the presence of an oxidizin~ agent at r~action conditions have becomewcll known and widely practic0d in the p~roleum refinin~ industry. These pro-cesses are typically designed to ~ffsct th~ sxidation of offensive mercaptans contained in a sour hydrocarbon fraction to innocuous disulfides - a process commonly re~0rred to as sweetening. The oxidizing agent is mos~ often air.
o Gasoline, including natural, straight run and cracked gasolinesj is the rnost fre-quently treated sour hydrocarbon fraction. Other sour hydrocarbon fractions which can be treated include 2he normally gaseous petroleum fraction as well as naphtha, kerosene, Jet fuel, fuel oil, and th~ like.
A commoniy used eon~inuous process for catalytically treatiny sour 15 hydrocarbon ~ractions entails contacting the fraction with a metal phthalocyanine catalyst dispersed in an aqusous caustic solution to yield a doctor sweet product. The sour fraction and the catalyst containing aqueous caustic solution provide a liquid-liquid system wherein mercaptans are converted to disulfidss at the interface of the immisGible solutions in the 20 presence of an oxidizing agen~--usually air. The prior art shows that catalysts such as metal phthalocyanines can b~ used to oxidize th~ m~rcaptans. ~, .~, U.S. Patent No. 2,999,806.
It has b~en ~ound that adding a quaternary ammonium compound to the caustic or alkaline solution used in such a process enhances the ability of the 25 oxidation catalyst to convert the mercaptans to disulfides. In particular, applicants have discovered that a preferred quaternary ammonium compound is a surfactant ~uaternary ammonium compound. Althou~h quaternary ammonium compounds have heretofor~ been used in sweetening sour hydrocarbon ~ractions, they have been used in eonjunction with fixed bed 30 catalysts, ~.g., a metal phthalocyanine dspositcd on an activated charcoal.
;"
.
.
.
.
2 ~
See. ~., U.S. Patsnt Nos. 4,156,641, 49124,494, 4,2~0,479 and ~,203,827.
There is no mention in the prior art of a quaternary ammonium compound bein0 used in ~olution with an oxidation c~alyst to oxidizs marcaptans to disuffides In a liquid/liquid systcm.
It has now also been discovered that there is a synergism bahNeen ths quaterna~ ammonium compountJ and tha oxidation catalyst, ~.~., m~tal phthalocyanine. That is, the enhancement In oxidation rats is lar~r than th~
sum of the rate for ~he oxidation catalyst and th~ quaternary ammonium com-pounds.
SU.MMARY OF THE INVENTIQ~
It is a broad objective of this invention to present an improved liquid/liquid process for catalytically treating a sour hydrocarbon frac~ion containing mercaptans. Thus, one broad embodiment of the invention is a catalytic process for sweetening a sour hydrocarbon fraction containin~
mercaptans comprising contacting ths hydrocarbon fraction in the presence of an oxidizing agent with an alkaline solution containing a metal chclate catalystwhersin the improvement involves adding to ~he alkaline solution a quaternary ammonium compound having the structural formula +
2 5 [ R~ ]
where R is a hydrocarbon group containing up to about 20 carbon atoms and selacted ~rom the group consisting of slkyl, cycloalkyl, aryl, alkaryl, and ~ralkyl;
Rl is a straight chain alkyl group containing from about 5 to about 20 carborl atoms, R2 is a hydrocarbon ~roup selected from the group consisting of aryl, 3c alkaryl and aralkyl; and X is an anion sel~cted from the group consis~in~ of halide, hydroxide, nitrate, sulfate, pho~phate, acetate, citrate ancl tarlr~te.
Other objects and smbodiments of this invention will become apparant in tha ~ollowing detailed description.
2 ~
See. ~., U.S. Patsnt Nos. 4,156,641, 49124,494, 4,2~0,479 and ~,203,827.
There is no mention in the prior art of a quaternary ammonium compound bein0 used in ~olution with an oxidation c~alyst to oxidizs marcaptans to disuffides In a liquid/liquid systcm.
It has now also been discovered that there is a synergism bahNeen ths quaterna~ ammonium compountJ and tha oxidation catalyst, ~.~., m~tal phthalocyanine. That is, the enhancement In oxidation rats is lar~r than th~
sum of the rate for ~he oxidation catalyst and th~ quaternary ammonium com-pounds.
SU.MMARY OF THE INVENTIQ~
It is a broad objective of this invention to present an improved liquid/liquid process for catalytically treating a sour hydrocarbon frac~ion containing mercaptans. Thus, one broad embodiment of the invention is a catalytic process for sweetening a sour hydrocarbon fraction containin~
mercaptans comprising contacting ths hydrocarbon fraction in the presence of an oxidizing agent with an alkaline solution containing a metal chclate catalystwhersin the improvement involves adding to ~he alkaline solution a quaternary ammonium compound having the structural formula +
2 5 [ R~ ]
where R is a hydrocarbon group containing up to about 20 carbon atoms and selacted ~rom the group consisting of slkyl, cycloalkyl, aryl, alkaryl, and ~ralkyl;
Rl is a straight chain alkyl group containing from about 5 to about 20 carborl atoms, R2 is a hydrocarbon ~roup selected from the group consisting of aryl, 3c alkaryl and aralkyl; and X is an anion sel~cted from the group consis~in~ of halide, hydroxide, nitrate, sulfate, pho~phate, acetate, citrate ancl tarlr~te.
Other objects and smbodiments of this invention will become apparant in tha ~ollowing detailed description.
2 ~
DETAILED DESC:RIPTIC)N OF THE~ INVEI~ION
~ he process of thi invention comprises contacting a sour hydrocarbon fraction in the presencs Qf an oxidizin~ ag~nt with an alkalin0 solu~ion con~aining a metal chelate catalyst and a quat~rnary ammonium compound.
5 ~he alkaline solution is an aqueous solution containing from about 0.1 to about 25 weight percent, preferably from about 0.1 to abou~ 10 weight percent, and most preferably from about 0.5 to about 7 weight percent of an alkali me~al hy-droxids. Sodium and potassiurn hydroxides are pref3rred, although ldhium hy-droxide, rubidium hydroxide and cesium hydroxide may also be used. The lO metal chelate employed In the practice of this invention can be any of the vari-ous metal chelates known ~o the art as effective in catalyzîng the oxidation of mercaptans contained in a sour petroleum distillate, to disulfides or polysul-fides. The metal chelates include the metal compounds of tetrapyridino-porphyrazine described in U.S. Patent No. 3,980,582, e.~., cobalt tetrapyridino-15 porphyrazine; porphyrin and metaloporphyrin catalysts as described in U.S.Patent No. 2,966,453, e.g., cobalt tetraphenylporphyrin sulfonate; corrinoid cat-alysts as described in U.S. Patent No. 3,252,892, B.9., cobalt corrin suHonate;
chelate organometallic catalysts such as described in U.S. Patent No.
2,918,426, e.g., the condensation product of an aminophenol and a metal of 20 Group Vlll; the metal phthalocyanines as described in U.S. Patent No.
~ he process of thi invention comprises contacting a sour hydrocarbon fraction in the presencs Qf an oxidizin~ ag~nt with an alkalin0 solu~ion con~aining a metal chelate catalyst and a quat~rnary ammonium compound.
5 ~he alkaline solution is an aqueous solution containing from about 0.1 to about 25 weight percent, preferably from about 0.1 to abou~ 10 weight percent, and most preferably from about 0.5 to about 7 weight percent of an alkali me~al hy-droxids. Sodium and potassiurn hydroxides are pref3rred, although ldhium hy-droxide, rubidium hydroxide and cesium hydroxide may also be used. The lO metal chelate employed In the practice of this invention can be any of the vari-ous metal chelates known ~o the art as effective in catalyzîng the oxidation of mercaptans contained in a sour petroleum distillate, to disulfides or polysul-fides. The metal chelates include the metal compounds of tetrapyridino-porphyrazine described in U.S. Patent No. 3,980,582, e.~., cobalt tetrapyridino-15 porphyrazine; porphyrin and metaloporphyrin catalysts as described in U.S.Patent No. 2,966,453, e.g., cobalt tetraphenylporphyrin sulfonate; corrinoid cat-alysts as described in U.S. Patent No. 3,252,892, B.9., cobalt corrin suHonate;
chelate organometallic catalysts such as described in U.S. Patent No.
2,918,426, e.g., the condensation product of an aminophenol and a metal of 20 Group Vlll; the metal phthalocyanines as described in U.S. Patent No.
4,290,913, etc. As stated in U.S. Patent 4,290,913, metal phthalocyanines are a preferred class of metal chelates. All the above-named patents are incorpo-rated herein by r0ference.
The metal ph~halocyanines which can be smployed to catalyzs the oxi-25 dation of mercaptans generally include magnesium phthalocyanine, titaniurn phthalocyanine, hafnium phthalocyanine, vanadium phthalocyanine, tantalum phthalocyanine, molybdenurn phthalocyanine, manganese ph~halocyanine, iron phthalocyanine, cobalt phthalocyanine, platinum ph~halocyanine, palladium phthalocyanine, copper phthalocyanine, silver phthalocyanine, zinc phthalo-3c cyanine, tin phthalocyanine, and the like. Cobalt phthalocyanine and vanadiumphthalocyanine are particularly preferred. The ring substituted metal phthalo-cyanines are generally employed in preference to the unsubstituted metal phthalocyanine (ses IJ.S. Paten~ 4,290,913), with the sulfonated matal phthalo-cyanine being especially preferred, e.g., cobalt phthalocyanine monosulfate, 35 cobalt phthalocyanine disulfonate, etc. The sulfonated derivatives may be pre-pared, for example, by reacting cobalt, vanadium or other metal phthalocyanine with fumin~ suHuric acid. Whil~ ~he suHonated derivativas ars preferrsd, it is un-darstood that oth~r d~rivstivss, particularly ~h~ carboxylat~d d0rivativ~s, may b~
employod. Th~ carboxylatcd d~rivativ~s ar~ rsa~ily prepared by thc action of tricllloroac~tic ~cid on tha mctal phthalor yanin~. The conoentrati~n of met~l 5 ch~late and m~tal phthalocyanine can vary from about 0.1 to about 2000 ppm and preferably from about 50 to about 800 ppm.
The quat~rnary ammonium compound which may be us~d has tha for-mula r 12 ¦. Rl--N--R ¦ X
R
15 where R i~ a hydrocarbon ~roup containin~ up to absut 20 carbon atoms and select~d from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl;
Rl is a straight chain alkyl group containing from about 5 to about 20 carbon atoms; R2 is a hydrocarbon group sr~lected from the ~roup consisting of aryl, alkaryl and aralkyl; and X is an anion selectcd from ths ~roup consisting of 20 halid~, hydroxide, nitrate, sulfate, phosphate, acetat~, citrate and tartrate. Illus-trative examples of the quaternary ammonium compounds which can be used to practice this invention, but which ar~ not intsnded to limit th0 scope of this in-vention are: benzyldimethyldodr cylammonium hydroxide, benzyldim~thyl-tetradecylammonium hydroxide, benzyldimethylhexadecylammonium hydrox-25 ide, benzyldimethyloctadecylammonium hydroxide, dimathylcyclohexyl-octylammonium hydroxide, diethylcyclohexyloctylammonium hydroxide, dipropylcyclohexyloctylammonium hydroxide, dimethylcyclohexyldecylammo-nium hydroxide, diethylcyclohexyldecylammonium hydroxid~, dipropylcyclo-hexyldecylammonium hydroxid2, dimethylcyclohexyldodecylammonium hy-3 0 droxide, diethylcyclohexyldodecylammonium hydroxide, dipropylcycloh~xyl-dodecylammonium hydroxide, dimethylcyclohexyltetradecylammonium hy-droxide, diethylcyclohexyltetradecylammonium hydroxide, dipropylcyclohexyl-tetradecylammonium hydroxide, dirnethylcyclohexylhexadecylammonium hy-droxide, disthylcyclohexylhexadecylammonium hydroxide, dipropylcyolohexyl-3 5 hexadecylammonium hydroxide, dimethylcyclohexyloctadecylammQnium hy-droxide, diethylcyclohexyloctadecylammonium hydroxide, dipropylcyclohexyl-octadecylammonium hydroxide, as well as ~h~ corresponding fluoride, chlorid~, bromide, iodide, sulfate, nitrate, nitrite, phosphate, acetate, citrats and tartrate compounds. rhe hydroxide eompounds are preferred and sspeciaily preferred hydroxides are benzyldimethyldodecylammonium hydroxide, benzyldimethyl-tetradecylammonium hydroxide, benzyldimethylhexadecylammonium hydroxide and benzyldimethyloctadecylammonium hydroxide. The concHntration of qua-5 ternary ammonium compound in ~he alkalin~ solution can vary from about 1 toabout 5000, prsferably from about 2 to about 100 ppm, and most preferably from about 5 to about 20 ppm.
As stated, preferred quaternary ammonium compounds ars surfactant quaternary ammonium compounds. By surfactant is meant a compound that lO has a critical micelle concentration (CMC) of iess than 0.2 molar, that is, the minimum amount for micelle formation in aqueous solution. Exarnples of ammonium quaternary compounds and their CMC are presented in Table A.
TABLE A
COMPOUND CMC (MOLAR) Hexadecyltrimethylammonium bromicle 0.0009 Dodecyltrimethylammonium bromide 0.0156 Octyltrimethylammonium bromide 0.13 Hexyltrimethylammonium bromide û.22 Sweetening of the sour hydrocarbon fraction is effected by oxidation of mcrcaptans. Accordingly, an oxidizing agent is necessary f~)r th~ reaction to proceed. Air is a preferred oxidizing agent, although oxygen or o~her oxyg0n-containing gases may be used. At least a stoichiometric amount of oxygen (relative to the concentration of mercaptans) is required to oxidize the mercap 25 tans to disulfides, although an excess amount of oxygen is usually employed. In some cases thc sour hydrocarbon fraction may contain entrained air or oxyg~n in sufficient concentration to accomplish th~ desired sweetenin~, but generally it is preferred to introduce air into the reaction zone.
Sweetening of th~ sour hydrocarbon fraction may be effected in any 30 suitable manner well known in the art and may be in a batch or continuous process. In a batch proc~ss the sour hydrocarbon fraction is introduced into a 2 ~
The metal ph~halocyanines which can be smployed to catalyzs the oxi-25 dation of mercaptans generally include magnesium phthalocyanine, titaniurn phthalocyanine, hafnium phthalocyanine, vanadium phthalocyanine, tantalum phthalocyanine, molybdenurn phthalocyanine, manganese ph~halocyanine, iron phthalocyanine, cobalt phthalocyanine, platinum ph~halocyanine, palladium phthalocyanine, copper phthalocyanine, silver phthalocyanine, zinc phthalo-3c cyanine, tin phthalocyanine, and the like. Cobalt phthalocyanine and vanadiumphthalocyanine are particularly preferred. The ring substituted metal phthalo-cyanines are generally employed in preference to the unsubstituted metal phthalocyanine (ses IJ.S. Paten~ 4,290,913), with the sulfonated matal phthalo-cyanine being especially preferred, e.g., cobalt phthalocyanine monosulfate, 35 cobalt phthalocyanine disulfonate, etc. The sulfonated derivatives may be pre-pared, for example, by reacting cobalt, vanadium or other metal phthalocyanine with fumin~ suHuric acid. Whil~ ~he suHonated derivativas ars preferrsd, it is un-darstood that oth~r d~rivstivss, particularly ~h~ carboxylat~d d0rivativ~s, may b~
employod. Th~ carboxylatcd d~rivativ~s ar~ rsa~ily prepared by thc action of tricllloroac~tic ~cid on tha mctal phthalor yanin~. The conoentrati~n of met~l 5 ch~late and m~tal phthalocyanine can vary from about 0.1 to about 2000 ppm and preferably from about 50 to about 800 ppm.
The quat~rnary ammonium compound which may be us~d has tha for-mula r 12 ¦. Rl--N--R ¦ X
R
15 where R i~ a hydrocarbon ~roup containin~ up to absut 20 carbon atoms and select~d from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl;
Rl is a straight chain alkyl group containing from about 5 to about 20 carbon atoms; R2 is a hydrocarbon group sr~lected from the ~roup consisting of aryl, alkaryl and aralkyl; and X is an anion selectcd from ths ~roup consisting of 20 halid~, hydroxide, nitrate, sulfate, phosphate, acetat~, citrate and tartrate. Illus-trative examples of the quaternary ammonium compounds which can be used to practice this invention, but which ar~ not intsnded to limit th0 scope of this in-vention are: benzyldimethyldodr cylammonium hydroxide, benzyldim~thyl-tetradecylammonium hydroxide, benzyldimethylhexadecylammonium hydrox-25 ide, benzyldimethyloctadecylammonium hydroxide, dimathylcyclohexyl-octylammonium hydroxide, diethylcyclohexyloctylammonium hydroxide, dipropylcyclohexyloctylammonium hydroxide, dimethylcyclohexyldecylammo-nium hydroxide, diethylcyclohexyldecylammonium hydroxid~, dipropylcyclo-hexyldecylammonium hydroxid2, dimethylcyclohexyldodecylammonium hy-3 0 droxide, diethylcyclohexyldodecylammonium hydroxide, dipropylcycloh~xyl-dodecylammonium hydroxide, dimethylcyclohexyltetradecylammonium hy-droxide, diethylcyclohexyltetradecylammonium hydroxide, dipropylcyclohexyl-tetradecylammonium hydroxide, dirnethylcyclohexylhexadecylammonium hy-droxide, disthylcyclohexylhexadecylammonium hydroxide, dipropylcyolohexyl-3 5 hexadecylammonium hydroxide, dimethylcyclohexyloctadecylammQnium hy-droxide, diethylcyclohexyloctadecylammonium hydroxide, dipropylcyclohexyl-octadecylammonium hydroxide, as well as ~h~ corresponding fluoride, chlorid~, bromide, iodide, sulfate, nitrate, nitrite, phosphate, acetate, citrats and tartrate compounds. rhe hydroxide eompounds are preferred and sspeciaily preferred hydroxides are benzyldimethyldodecylammonium hydroxide, benzyldimethyl-tetradecylammonium hydroxide, benzyldimethylhexadecylammonium hydroxide and benzyldimethyloctadecylammonium hydroxide. The concHntration of qua-5 ternary ammonium compound in ~he alkalin~ solution can vary from about 1 toabout 5000, prsferably from about 2 to about 100 ppm, and most preferably from about 5 to about 20 ppm.
As stated, preferred quaternary ammonium compounds ars surfactant quaternary ammonium compounds. By surfactant is meant a compound that lO has a critical micelle concentration (CMC) of iess than 0.2 molar, that is, the minimum amount for micelle formation in aqueous solution. Exarnples of ammonium quaternary compounds and their CMC are presented in Table A.
TABLE A
COMPOUND CMC (MOLAR) Hexadecyltrimethylammonium bromicle 0.0009 Dodecyltrimethylammonium bromide 0.0156 Octyltrimethylammonium bromide 0.13 Hexyltrimethylammonium bromide û.22 Sweetening of the sour hydrocarbon fraction is effected by oxidation of mcrcaptans. Accordingly, an oxidizing agent is necessary f~)r th~ reaction to proceed. Air is a preferred oxidizing agent, although oxygen or o~her oxyg0n-containing gases may be used. At least a stoichiometric amount of oxygen (relative to the concentration of mercaptans) is required to oxidize the mercap 25 tans to disulfides, although an excess amount of oxygen is usually employed. In some cases thc sour hydrocarbon fraction may contain entrained air or oxyg~n in sufficient concentration to accomplish th~ desired sweetenin~, but generally it is preferred to introduce air into the reaction zone.
Sweetening of th~ sour hydrocarbon fraction may be effected in any 30 suitable manner well known in the art and may be in a batch or continuous process. In a batch proc~ss the sour hydrocarbon fraction is introduced into a 2 ~
reaction zone containin9 the alkaline solution which contains the metal chelate snd the quaternary ammoniurn compound. Air is introduced thcrein or pass~d th0rethrough. Preferably the reaction zone is equipped with suitabl~ stirrers orothsr mixing devices to obtain intimate mixing. In a continuaus process thc s alkalinc solution containing the metal chelate catalyst and the quaternary ammonium compounds is passed countercurrently or concurrently with the sour hydrocarbon fraction in the presenc~ of a continuous stream of air. In a mixed type process, the rgaction zone contains ~h~ alkaline solution, metal chelate and quat~rnary ammonium compound, and gasoline and air ar lO continuously passed therathrough and removed generally trom ~he upper portion of the reaction zone. For specifie examples of apparatus used to carry out a liquid/liquid process, see U.S. Patent Nos. 4,019,869, 4,201,626 and 4,234,544 which are incorporated by reference.
In general the process is usually effected at ambient temperatures, al-15 though elevated temperatures may be employed and generally will be in the range of from 38 to 204C (100 to abou~ 400F), depending upon the pressure utilized therein, but usually below that at which substantial vaporization occurs. Pressures of up to 6895 kPa (1,000 psi) or more are operable although atmospheric or substantially atmospheric pressures are suitable.
The following examples are presented in illustration of this invention and are not intended as undue limitations on the generally broad scope of the in-vention as set out in the appended claims.
EXAMPLE I
A stirred contactor which consisted of a cylindrical glass container mea-suring 8.9 mm (3.5 inches) in diameter by 15.2 mm (6 inches) high and which contained 4 baffles that are at 90 angles to the side walls w~s used. An air driven motor was used to power a paddle stirrer positioned in the center of the apparatus. When turning, the stirrer paddles passed within 1.3 mm (1/2 inch) of the baffles. This resuited in a very efficient, purc type of mixin~.
3c To the above apparatus there were added 50 milliliters of a 7% aqucous sodium hydroxide solution which contained 30 weight ppm of a caustic soiuble tctrasulfonated cobalt phthalocyanine and 200 milliliters of isooctane which contained 1,300 weight ppm of mercaptan sulfur as n~octylmercaptan. To this mixture an amount of a quaternary ammonium compound was added and the mixture was stirr~d. Periodically stirring was stopped ~nd a sample was withdrawn from Ihe isooctane layer with a pipette. These samples were analyzed for mercaptan by ti~ration. During the tests reported in Table 1, the apparatus was maintained at 21.7C and 1 atmosphere.
The above experiment was repeated several times with varying amounts 5 of a quaternary amrnonium compound and with various quat~rnary ammonium compounds. These results are pr0santed in Table 1.
Table 1 Effect ~ Quaternary Ammonium Compound lC on Mercaptan Oxidation _ Percent Mercaptan Quatarnary Concentration CoPc1 Conversion After Compound wt ppm wt ppm 90 Minutes of Contact None - 30 38 MaquatTM TC-76 10 30 80 MaquatTM T(::-76 20 30 77 MaquatTM TC-76 20 0 18 sumquatTM2311 20 30 42 20 SumquatTM 2311 6û 30 45 ` .
MaquatlrM TC-76 is a mixture of mono- and dimethyl, dialkyl and alkylbenzylammonium chlorides. The alkyl ~roups ara primarily C14 groups although other chain length groups are also pres~nt. Befor~ us~
the MaquatTM TC-76 was conv~rted to the hydroxide form by ion exchange. Maquat~M TC-76 is a tradenam0 of the Mason Ch0mical Company of Chicago, IL
- 2~11&4~
In general the process is usually effected at ambient temperatures, al-15 though elevated temperatures may be employed and generally will be in the range of from 38 to 204C (100 to abou~ 400F), depending upon the pressure utilized therein, but usually below that at which substantial vaporization occurs. Pressures of up to 6895 kPa (1,000 psi) or more are operable although atmospheric or substantially atmospheric pressures are suitable.
The following examples are presented in illustration of this invention and are not intended as undue limitations on the generally broad scope of the in-vention as set out in the appended claims.
EXAMPLE I
A stirred contactor which consisted of a cylindrical glass container mea-suring 8.9 mm (3.5 inches) in diameter by 15.2 mm (6 inches) high and which contained 4 baffles that are at 90 angles to the side walls w~s used. An air driven motor was used to power a paddle stirrer positioned in the center of the apparatus. When turning, the stirrer paddles passed within 1.3 mm (1/2 inch) of the baffles. This resuited in a very efficient, purc type of mixin~.
3c To the above apparatus there were added 50 milliliters of a 7% aqucous sodium hydroxide solution which contained 30 weight ppm of a caustic soiuble tctrasulfonated cobalt phthalocyanine and 200 milliliters of isooctane which contained 1,300 weight ppm of mercaptan sulfur as n~octylmercaptan. To this mixture an amount of a quaternary ammonium compound was added and the mixture was stirr~d. Periodically stirring was stopped ~nd a sample was withdrawn from Ihe isooctane layer with a pipette. These samples were analyzed for mercaptan by ti~ration. During the tests reported in Table 1, the apparatus was maintained at 21.7C and 1 atmosphere.
The above experiment was repeated several times with varying amounts 5 of a quaternary amrnonium compound and with various quat~rnary ammonium compounds. These results are pr0santed in Table 1.
Table 1 Effect ~ Quaternary Ammonium Compound lC on Mercaptan Oxidation _ Percent Mercaptan Quatarnary Concentration CoPc1 Conversion After Compound wt ppm wt ppm 90 Minutes of Contact None - 30 38 MaquatTM TC-76 10 30 80 MaquatTM T(::-76 20 30 77 MaquatTM TC-76 20 0 18 sumquatTM2311 20 30 42 20 SumquatTM 2311 6û 30 45 ` .
MaquatlrM TC-76 is a mixture of mono- and dimethyl, dialkyl and alkylbenzylammonium chlorides. The alkyl ~roups ara primarily C14 groups although other chain length groups are also pres~nt. Befor~ us~
the MaquatTM TC-76 was conv~rted to the hydroxide form by ion exchange. Maquat~M TC-76 is a tradenam0 of the Mason Ch0mical Company of Chicago, IL
- 2~11&4~
SumquatTM 2311 is trimethylbenzyl amrnonium hydroxide which is a non-sur~actant quaternary ammonium hydrs:~xide. SumquatTM is a trads mark of thc Hexcel Corporation of Z0eland, Michigan.
5 1 CoPC is a tetrasulfonated cobal~ phthalocyanine.
The data presented in Table 1 clearly show that addition of a quaternary ammonium hydroxide enhances the ability of the cobalt phthalocyanine catalyst to oxidize mercaptans to disu~ldes. It is also observed that a surfactant lO quaternary ammonium hydroxide enhances ~he oxidation of mercaptans to much greater extent than a non-surfactant quaternary ammonium compound.
-, ~ - , , , ,
5 1 CoPC is a tetrasulfonated cobal~ phthalocyanine.
The data presented in Table 1 clearly show that addition of a quaternary ammonium hydroxide enhances the ability of the cobalt phthalocyanine catalyst to oxidize mercaptans to disu~ldes. It is also observed that a surfactant lO quaternary ammonium hydroxide enhances ~he oxidation of mercaptans to much greater extent than a non-surfactant quaternary ammonium compound.
-, ~ - , , , ,
Claims (5)
1. A process for catalytically sweetening a sour hydrocarbon fraction containing mercaptans comprising contacting the hydrocarbon fraction in the presence of an oxidizing agent with an alkaline solution containing a metal chelate further characterized in that the alkaline solution has added thereto a quaternary ammonium compound having the structural formula where R is a hydrocarbon group containing up to about 20 carbon atoms and selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl, R1 is a straight chain alkyl group containing from about 6 to about 20 carbon atoms, R2 is a hydrocarbon group selected from the group consisting of aryl, alkaryl and aralkyl and X is an anion selected from the group consisting of halide, hydroxide, nitrate, sulfate, phosphate, acetate, citrate and tartrate.
2. The process of Claim 1 further characterized in that the metal chelate is a metal phthalocyanine.
3. The process of Claim 2 further characterized in that the alkaline solution is a sodium hydroxide solution containing from about 0.1 to about 25 weight percent sodium hydroxide, in that the metal phthalocyanine is a cobalt phthalocyanine and is present in a concentration from about 0.1 to about 2000 ppm, and in that the quaternary ammonium compound is present in a concentration from about 1 to about 5000 ppm.
4. The process of Claim 2 or 3 further characterized in that the quaternary ammonium compound is a surfactant quaternary ammonium compound.
5. The process of any one of Claims 1 to 4 where X is an hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/354,966 US4923596A (en) | 1989-05-22 | 1989-05-22 | Use of quaternary ammonium compounds in a liquid/liquid process for sweetening a sour hydrocarbon fraction |
| US354,966 | 1989-05-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2016416A1 true CA2016416A1 (en) | 1990-11-22 |
Family
ID=23395657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002016416A Abandoned CA2016416A1 (en) | 1989-05-22 | 1990-05-09 | Liquid/liquid catalytic sweetening process |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4923596A (en) |
| EP (1) | EP0399702A1 (en) |
| JP (1) | JPH0643586B2 (en) |
| KR (1) | KR930011064B1 (en) |
| CN (1) | CN1022042C (en) |
| AU (1) | AU629930B2 (en) |
| CA (1) | CA2016416A1 (en) |
| ZA (1) | ZA903748B (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039398A (en) * | 1990-03-19 | 1991-08-13 | Uop | Elimination of caustic prewash in the fixed bed sweetening of high naphthenic acids hydrocarbons |
| US5180484A (en) * | 1990-08-27 | 1993-01-19 | Uop | Caustic free liquid/liquid process for sweeting a sour hydrocarbon fraction |
| US5093296A (en) * | 1990-08-27 | 1992-03-03 | Uop | Caustic free liquid/liquid process for sweetening a sour hydrocarbon fraction |
| US5273646A (en) * | 1990-08-27 | 1993-12-28 | Uop | Process for improving the activity of a mercaptan oxidation catalyst |
| US5204306A (en) * | 1990-08-27 | 1993-04-20 | Uop | Caustic free catalyst for use in a liquid/liquid process for sweetening a sour hydrocarbon fraction |
| US5200062A (en) * | 1991-06-17 | 1993-04-06 | Exxon Research And Engineering Company | Process for removing elemental sulfur from fluids |
| US6488840B1 (en) * | 2000-04-18 | 2002-12-03 | Exxonmobil Research And Engineering Company | Mercaptan removal from petroleum streams (Law950) |
| US7223332B1 (en) | 2003-10-21 | 2007-05-29 | Uop Llc | Reactor and process for mercaptan oxidation and separation in the same vessel |
| JP4655509B2 (en) * | 2004-05-13 | 2011-03-23 | 住友化学株式会社 | Contact treated product, catalyst component for addition polymerization, catalyst for addition polymerization, and method for producing addition polymer |
| JP4709737B2 (en) * | 2006-12-27 | 2011-06-22 | 花王株式会社 | Hair straightening composition |
| JP4769947B2 (en) * | 2007-03-02 | 2011-09-07 | 国立大学法人神戸大学 | Pointing system and pointing method |
| US20080230445A1 (en) * | 2007-03-19 | 2008-09-25 | Baker Hughes Incorporated | Method of scavenging mercaptans from hydrocarbons |
| US8679203B2 (en) * | 2007-03-19 | 2014-03-25 | Baker Hughes Incorporated | Method of scavenging mercaptans from hydrocarbons |
| RU2458968C1 (en) * | 2011-02-09 | 2012-08-20 | Ооо "Фотохим" | Catalytic composition for demercaptanisation of oil and oil products |
| CN102513160B (en) * | 2011-11-29 | 2013-04-03 | 长春惠工净化工业有限公司 | Mercaptan oxidative conversion catalyst for fixed bed gasoline and preparation method thereof |
| CN103374382B (en) * | 2012-04-26 | 2015-05-20 | 中国石油化工股份有限公司 | Method for deodorizing light oil |
| CN103768913B (en) * | 2012-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of method removing hydrogen sulfide and mercaptan in gas |
| CN104549337B (en) * | 2013-10-15 | 2017-01-25 | 中国石油化工股份有限公司 | Oxidation catalyst for mercaptan in light oil, as well as preparation method and application of mercaptan oxidation catalyst |
| CN104588097B (en) * | 2013-10-30 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for mercaptol oxidization |
| WO2017011242A1 (en) | 2015-07-15 | 2017-01-19 | Uop Llc | Oxidation catalyst and processes for using same |
| RU2656100C2 (en) * | 2016-11-21 | 2018-05-31 | Закрытое акционерное общество "ИВКАЗ" | Catalytic composition for oil and gas condensate demercaptanisation |
| CN110628475B (en) * | 2018-06-21 | 2020-11-13 | 中国石油化工股份有限公司 | Process for pretreating rich gas in refinery and process for desulfurizing dry gas and/or liquefied gas |
| CN110628476B (en) * | 2018-06-21 | 2020-11-13 | 中国石油化工股份有限公司 | Pretreatment method and purifying agent for refinery rich gas and desulfurization method for dry gas and/or liquefied gas |
| RU2750214C1 (en) * | 2020-10-01 | 2021-06-24 | Общество с ограниченной ответственностью "Синтез" | Catalyst composition for oxidative demercaptanization of oil and oil products |
Family Cites Families (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL103100C (en) * | 1957-05-10 | |||
| US2966453A (en) * | 1959-03-13 | 1960-12-27 | Universal Oil Prod Co | Oxidation of mercapto compounds |
| US2999806A (en) * | 1959-03-13 | 1961-09-12 | Universal Oil Prod Co | Treatment of hydrocarbon distillates |
| US3252892A (en) * | 1964-09-22 | 1966-05-24 | Universal Oil Prod Co | Oxidation of mercapto compounds using corrinoid catalyst |
| US3980582A (en) * | 1973-09-07 | 1976-09-14 | Ashland Oil, Inc. | Method and catalyst for removing mercaptans and mercaptide compounds from aqueous alkaline solutions |
| US4019869A (en) * | 1975-11-10 | 1977-04-26 | Uop Inc. | Combination reactor-separator apparatus |
| US4124494A (en) * | 1978-01-11 | 1978-11-07 | Uop Inc. | Treating a petroleum distillate with a supported metal phthalocyanine and an alkanolamine hydroxide |
| US4124493A (en) * | 1978-02-24 | 1978-11-07 | Uop Inc. | Catalytic oxidation of mercaptan in petroleum distillate including alkaline reagent and substituted ammonium halide |
| US4290913A (en) * | 1978-07-24 | 1981-09-22 | Uop Inc. | Catalytic composite useful for the treatment of mercaptan-containing sour petroleum distillate |
| US4201626A (en) * | 1978-08-24 | 1980-05-06 | Uop Inc. | Liquid-liquid contacting apparatus |
| US4203827A (en) * | 1978-08-28 | 1980-05-20 | Uop Inc. | Process for treating sour petroleum distillates |
| US4308169A (en) * | 1978-12-26 | 1981-12-29 | Uop Inc. | Method of reactivating a catalytic composite of a carrier material and a mercaptan oxidation catalyst |
| US4234544A (en) * | 1979-06-25 | 1980-11-18 | Uop Inc. | Liquid-liquid extraction apparatus |
| US4260479A (en) * | 1979-09-27 | 1981-04-07 | Uop Inc. | Catalytic oxidation of mercaptan in sour petroleum distillate |
| US4290916A (en) * | 1979-10-01 | 1981-09-22 | Uop Inc. | Catalytic composite, method of manufacture, and process for use |
| US4324650A (en) * | 1979-10-01 | 1982-04-13 | Uop Inc. | Catalytic composite and process for use |
| US4276194A (en) * | 1979-10-01 | 1981-06-30 | Uop Inc. | Catalytic composite, method of manufacture, and process for use |
| US4337147A (en) * | 1979-11-07 | 1982-06-29 | Uop Inc. | Catalytic composite and process for use |
| US4354926A (en) * | 1980-01-04 | 1982-10-19 | Uop Inc. | Catalytic composite and process for use |
| US4298463A (en) * | 1980-07-11 | 1981-11-03 | Uop Inc. | Method of treating a sour petroleum distillate |
| US4360421A (en) * | 1980-07-17 | 1982-11-23 | Uop Inc. | Method for treating mercaptans contained in a sour petroleum distillate |
| US4574121A (en) * | 1983-11-29 | 1986-03-04 | Uop Inc. | Metal chelate mercaptan oxidation catalyst |
| US4498977A (en) * | 1983-11-29 | 1985-02-12 | Uop Inc. | Catalytic oxidation of mercaptan in petroleum distillate |
| US4502949A (en) * | 1984-02-15 | 1985-03-05 | Uop Inc. | Catalytic oxidation of mercaptan in petroleum distillate |
| US4753722A (en) * | 1986-06-17 | 1988-06-28 | Merichem Company | Treatment of mercaptan-containing streams utilizing nitrogen based promoters |
-
1989
- 1989-05-22 US US07/354,966 patent/US4923596A/en not_active Expired - Lifetime
-
1990
- 1990-05-01 AU AU54559/90A patent/AU629930B2/en not_active Expired
- 1990-05-09 CA CA002016416A patent/CA2016416A1/en not_active Abandoned
- 1990-05-10 EP EP90305059A patent/EP0399702A1/en not_active Ceased
- 1990-05-16 ZA ZA903748A patent/ZA903748B/en unknown
- 1990-05-18 JP JP2127028A patent/JPH0643586B2/en not_active Expired - Fee Related
- 1990-05-21 KR KR1019900007419A patent/KR930011064B1/en not_active IP Right Cessation
- 1990-05-22 CN CN90103718A patent/CN1022042C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU629930B2 (en) | 1992-10-15 |
| JPH0643586B2 (en) | 1994-06-08 |
| JPH03103491A (en) | 1991-04-30 |
| ZA903748B (en) | 1991-04-24 |
| AU5455990A (en) | 1990-11-22 |
| EP0399702A1 (en) | 1990-11-28 |
| KR900018337A (en) | 1990-12-21 |
| CN1022042C (en) | 1993-09-08 |
| US4923596A (en) | 1990-05-08 |
| KR930011064B1 (en) | 1993-11-20 |
| CN1047523A (en) | 1990-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2016416A1 (en) | Liquid/liquid catalytic sweetening process | |
| US4120865A (en) | Metal complex and method for preparing | |
| US4908122A (en) | Process for sweetening a sour hydrocarbon fraction | |
| IE47834B1 (en) | Process for treating sour petroleum distillates | |
| US5318936A (en) | Catalyst for sweetening a sour hydrocarbon fraction containing metal oxide solid solution and magnesium oxide | |
| US4913802A (en) | Process for sweetening a sour hydrocarbon fraction | |
| CA1241614A (en) | Catalytic oxidation of mercaptans in petroleum distillate | |
| US5273646A (en) | Process for improving the activity of a mercaptan oxidation catalyst | |
| CA2055779C (en) | Two step process for sweetening a sour hydrocarbon fraction | |
| CA1224771A (en) | Catalytic oxidation of mercaptan in petroleum distillate | |
| AU618886B2 (en) | Caustic-free sweetening of sour hydrocarbon streams | |
| EP0411762B1 (en) | Improved catalyst and process for sweetening a sour hydrocarbon stream | |
| US4897180A (en) | Catalytic composite and process for mercaptan sweetening | |
| US4243551A (en) | Catalyst for oxidizing mercaptans and mercaptide compounds and method for preparing | |
| US5180484A (en) | Caustic free liquid/liquid process for sweeting a sour hydrocarbon fraction | |
| US4290917A (en) | Method of manufacturing a catalytic composite | |
| US5093296A (en) | Caustic free liquid/liquid process for sweetening a sour hydrocarbon fraction | |
| US4295993A (en) | Catalytic composite, method of manufacture and process for use | |
| US4290916A (en) | Catalytic composite, method of manufacture, and process for use | |
| US4354926A (en) | Catalytic composite and process for use | |
| US4324650A (en) | Catalytic composite and process for use | |
| US4956324A (en) | Catalyst containing dipolar compounds useful for sweetening a sour hydrocarbon fraction | |
| US5204306A (en) | Caustic free catalyst for use in a liquid/liquid process for sweetening a sour hydrocarbon fraction | |
| CA1124223A (en) | Catalytic composite particularly useful for the oxidation of mercaptans contained in a sour petroleum distillate | |
| EP0119885B1 (en) | Process for the preparation of a catalyst for the oxidation of mercaptans to disulfides, and use of this catalyst in the sweetening of petroleum distillates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |